Process of effecting catalytic reactions.



UNITED STATES PATENT onrron.

o'rro CHRISTIAN HAGEMANN, or YONKERS, AND CHARLES nasxnnvrnnn, or NEWYORK, N. Y.

osaaso.

No Drawing.

Specification of Letters Patent.

Application filed February 8, 1913. Serial No. 747,181.

Patented Jan. 13, 1914.

To all whom it may concern:

Be it known that we, Or'ro CHRISTIAN HAGEMANN, a subject of the Kin ofGreat Britain, residing at Yonkers, ew York, and CHARLES BASKERVILLE acitizen of the United States, residing at flew York, N. Y., haveinvented new and useful Improvements in Processes of Effecting CatalyticReactions, of which the following is a specification.

The present invention relates to improve, ments in the art of catalysis.

A particularly novel feature in the catalytic process is the use of acatalytic metal, for example'nickel or cobalt in a particular physicalcondition, whereby it may be very effectively held in suspension, andalso whereby a small amount of nickel can be used to effect thecatalytic reaction on very large amounts of material. Moreover by theuse of this particular form of catalyst, the revivification thereofbecomes a very simple matter.

In the hydrogenation of fats, fatty oils, fatty acids and their esters,etc., as well as in the preparation of organic substitution products byhydrogenating or hydrogenizmg hr reduction processes, the variouscatalyzers, catalysis or contact substances used, such as finely dividednickel, cobalt, etc., are usually employed in a state of minutesubdivision, as in the form of a powder, obtained bythereduction of theoxid, hydroxid, carbonate, chlorid, etc., at an adequate temperature, bymeans of hydrogen, either alone or when precipitated upon some inert,absorptive, refractory carrier or medium as for example, kieselguhr,asbestos, etc. It has been demonstrated by Sabatier and Senderens, aswell as by a number of other investigators, that by the intervention orinfluence of such catalyzers, unsaturated fatty acids or their glyceridsmay be made to absorb hydrogen, thatis, to become hydrogenated, by whichmeans they become hardened, being converted into corresponding saturatedcompounds. However, t e application of those catalyzers involves anumber of serious technical drawbacks and difliculties; for instance, onaccount of their finely-divided state, they cannot be readily andsatisfactorily separated and recovered from the fats, fatty oils, fatt'acids, etc, and, owing to their density, t e said 65 catalyzers do notremain well suspended in the fat, oil, etc., treated, when suchsuspension is desired.

The use of ametal precipitated upon an inert carrier, such askieselguhr, has not given entirely satisfactory results, probably forthe reason that only a small part (one side) of the film of theprecipitated metal comes into actual contact with the liquid to bereduced and the hydrogen, and the remainder of the metal is consequentlyinactive, sincethe reacting materials cannot come into contacttherewith. Another serious objection to the use of such a catalyst isthat the process of revivifying the same is quite an expensiveundertaking, since the metal must be dissolved in an acid, andrepre'cipitated upon kieselguhr. Also it is rather diflicult to separatethe catalytic metal completely from the hydrogenized oil, Whether in theform of a fine powder or when deposited upon kieselguhr. It has beenalso found diflicul't to obtain a catalyzer by precipitation andreduction methods, which is free from oxids and other impurities. It hasbeen ascertained, moreover, that fats, fatty oils, etc., hydrogenatedwith such finely-di vided catalyzcrs will contain metallic soaps, suchas soaps having a nickel base, which are undesirable from economic andhygenic standpoints.

We have found that metals having catalytic activity, for example,nickel, or cobalt, brought into a state of extremely thin films, plates,leaves, or flakes by physical, mecha nical, chemical or galvanoplast-icprocesses, as, for example, by the method shown by Thomas A. Edison (U.S. Patent No. 865,688), offers many important technical advanta es ascatalysts in the hydrogenization of fats, fatty oils, fatty acids andtheir esters, as well as in effecting gas reactions. These films, platesor flakes are obtainable in a state of high purity, and'may be employedfor cata ytic purposes either in the metallic fipure) state or afterbeing partially oxi ized. These leaves or films can readily be prepared,having a thickness of from one twenty-thousandth to one fortythousandthof an inch, and accordingly the efficiency of a given weight a catalyticmetal, for example nickel, w en applied in this form, is very great,owing to the large amount of exposed surface. Such films, or flakes,will, on account of their extreme thinness, readily float and remainevenly dis- 7 have found that flaky metals tributed throughout the wholemass or volume of fats oils, fatty acids, etc., under treatment. In thetreatment of liquids with gases, as .well as in catalytic gasreact-ions, the process can be carried out underany desired amount ofpressure. Besides the application of such filmy, flaky, flocculentcatalysts in the hydrogenation of fats, fatty oils, fatty acids andtheir esters, etc.,'they may be used in such processes as the productionof methane from carbon dioxid, the elimination of carbon monoxid fromwatergas, and in other'gas reactions where nickel, etc, has been foundto be advantageous-as a catalyzer. These fine, flaky, lamellous films,orleaves of met-a1 being brought into contact with the hydrogen or othergases on both surfaces or sides, ofl'er singular advantages inhydrogenating, hydrogenizing, and reduction processes, and in effectinggas reactions wherein cobalt, nickel, etc., is a suitable catalyst. Inthe hydrogenation of fats, fatty oils, fatty acids, and their esters,etc, such metallic films or flakes, act as catalyzers of a reliable anduniform degree of activity. 7

In addition to the advantages offered by the extreme thinness of'themetal, which produces an extremely large surface, there is anothercharacteristic advantage which is worthy of note, namely that the leaveswill remain suspended in the oils, or other material under treatmentwith the greatest facility.

The separation of the finished hydrogen.

ated fats, oils, acids, etc., that is, the hardened or partiallyhardened products from the flaky nickel, cobalt, etc, is, we have found,accomplished without dilficulty, thus entirely obviating the serioustechnical drawbacks which lie in the recovery of the products from thecatalyzers in a pulverized state.

In the revivification and recovery of the catalyzer for subsequenthydrogenations, we as nickel, etc., admit of great economy, for theflakes retain their physical form. In this revivification we subject'theflakes, films, lamellae, leaves or plates, from which the fat, oil, etc,has been removed, (for example, by extraction with a suitable solvent)to a process of surface oxidation, followed by reduction with hydrogenat, say, 300 C. Said surface oxidation may be conveniently effected byheating to about 300 C., or higher, in a current of oxygen or air insuitable apparatus, or by treatment with oxidizing agents in liquids inwhich the metallic flakes are suspended. In such a manner, we areenabled to many times restore freshly reduced surfaces to both sides ofthe metal flakes or films, without having recourse to conversion of themetal into a soluble salt, precipitating, igniting, and reducing. Thusit will be seen that by the use of these extremely thin plates or films,we can greatly cheapen the catalytic processes above referred to, andalso cheapen.

the process of revivifying the catalyst.

In the appended claims, the term leaves, is intended to cover flakes,films, lamellae, etc., of the kind above referred to, and this term isnot intended to cover a layer or film of ametal such as nickel,deposited upon and carried by the particles of a material such askieselguhr, pumice stone and the like, since as above stated theadvantages of the use, of they independently floating filmiferm bodiesare not secured by. the use of'a catalyst consisting of a film of metalcarried by an inert body.

What we, claim is y 1. In the art of effectingcatalytic reactions, thestep which comprises bringing t gether the reacting materials in thepresence of a catalytic metal in the form of very thin leaves.

2.-In the art of effecting catalytic reactions, the step which comprisesbringing together the reacting materials in the presence of a metal ofthe nickel group in the form of very thin leaves.

3. In the art of effecting catalytic reactions, the step which comprisesbringing together the reacting materials in the'presence of a metallicnickel in the form of very thin leaves.

4. In the art of effecting catalytic reactions, the step which comprlsesbringing together hydrogen and a material to be reduced thereby in thepresence of a catalytic metal in the form of very thin leaves.

5. In the art of eflecting catalytic reactions the step which comprisesbringing together hydrogen and a fatty body in the presenceof acatalytic metal in the form of very thin leaves. v H

6. In the art of effecting catalytic reactions, the step which comprisesbringing together hydrogen and an oil containing a glycerid of anunsaturated fatty acid in the presence of a catalytic metal in the formof verythin leaves.

7. In the art of effecting catalytic reactions, the step which comprisesbringing together the reacting materials in the presence of a catalyticmetal in the form of very thin leaves, having the surface thereofpartially oxidized.

Signed at New York city, this 7th day of February 1913..

OTTO CHRISTIAN HAGEMANN. CHARLES BASKERVILLE. Witnesses:

W. A. Hanson, THOMAS F. OKEEFFE.

